Ether carbinols

ABSTRACT

Described are ether carbinols defined according to the generic structure: ##STR1## wherein X 1  represents a moiety selected from the group consisting of: ##STR2## and wherein Y 1  represents C 4  or C 5  alkylene; C 4  or C 5  alkenylene or C 4  or C 5  alkynylene; processes for preparing such ether carbinols by means of first reacting allyl ethers with a mixture or carbon monoxide and hydrogen by means of an oxo reaction to produce ether carboxaldehydes and then reducing the thus formed ether carboxaldehydes to ether carbinols; or reacting camphene with appropriate diols; as well as methods for augmenting or enhancing the aroma or taste of consumable materials including perfumes, colognes and perfumed articles; foodstuffs, chewing gums, chewing tobaccos, medicinal products and toothpastes; and smoking tobaccos and smoking tobacco articles by adding thereto an aroma or taste augmenting or enhancing quantity of the thus produced ether carbinols. 
     Also described are two ether carboxaldehydes having one of the structures: ##STR3## processes for preparing such ether carboxaldehydes by means of reacting out an appropriate allyl ether with a mixture of carbon monoxide and hydrogen by means of an oxo-reaction as well as methods for augmenting or enhancing the aroma or taste of consumable materials including perfumes, colgnes and perfumed articles; foodstuffs, chewing gums, chewing tobaccos, medicinal products and toothpastes; smoking tobaccos and smoking tobacco articles by adding thereto an aroma or taste augmenting or enhancing quantity of the thus produced ether carboxaldehydes.

This is a divisional of application Ser. No. 644,054, filed 8/24/84which, in turn, is a stream-line divisional of Application for U.S.Letters Patent, Ser. No. 574,150 filed 1/26/84, now U.S. Pat. No.4,521,634 issued 6/4/85 which, in turn, is a continuation-in-part ofApplication for U.S. Letters Patent, Ser. No. 533,915 filed 9/19/83, nowU.S. Pat. No. 4,532,364 issued 7/30/85 which, in turn, is acontinuation-in-part of Application for U.S. Letters Patent, Ser. No.507,292 filed 8/1/83, now abandoned.

BACKGROUND OF THE INVENTION

The instant invention provides ether carbinols defined according to thegeneric structure: ##STR4## wherein X₁ represents a moiety selected fromthe group consisting of: ##STR5## and wherein Y₁ represents C₄ or C₅alkylene; C₄ or C₅ alkenylene or C₄ or C₅ alkynylene and in addition twoether carboxaldehydes defined according to the structures: ##STR6##

Inexpensive chemical compositions of matter which can provide nutty,woody, ozoney, fresh air dried clothing-like, green, orange, mint,patchouli-like, incense-like, oniony, garlic, lavender-like, herbaceous,leafy, pepper-like, spicy, camphoraceous, woody, floral, sweet fruityand chamomile-like aromas with patchouli-like, cedarwood, oniony,animalic sweaty, herbaceous, peppery, olibanum-like, diffusive amber,rosey and caramellic undertones are highly desirable in the art ofperfumery. Many of the natural materials which provide such fragrancesand contribute desired nuances to perfumery compositions as well asperfumed articles including solid or liquid anionic, cationic, nonionicor zwitterionic detergents, perfumed polymers, fabric softenercompositions, fabric softener articles, hair preparations, cosmeticpowders and the like are high in cost, vary in quality from one batch toanother and/or are generally subject to the usual variations of naturalproducts.

By the same token, materials which can provide nutty, patchouli-like,oriental, incense, musky, sandalwood, walnut-like, onion, garlic,floral, and fruity aromas and tastes are highly useful and are wellknown in the art of flavorings for foodstuffs, toothpastes, chewinggums, medicinal products and chewing tobaccos. Many of the naturalmaterials which provide such flavor nuances and contribute desirednuances to flavors and compositions are high in cost, vary in qualityfrom one batch to another and/or are generally subject to the usualvariations of natural products.

Materials which can provide woody, incense-like, oriental and patchouliaroma and taste nuances to smoking tobacco compositions and componentsof smoking tobacco articles prior to and on smoking in the main streamand in the side stream are highly desirable in the smoking tobacco art.Many of the natural materials which provide such flavor and aromanuances and contribute desired nuances to flavoring compositions forsmoking tobacco and smoking tobacco article components, e.g., filtersand wrappers as well as the main body of the tobacco, are high in cost,vary in quality from one batch to another and/or are generally subjectto the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the essential flavor andfragrance notes provided by natural essential oils or compositionscontaining the same. Unfortunately, many of the synthetic materialseither have the desired nuances only to a relatively small degree, orelse contribute undesirable or unwanted odor to the compositions. Thesearch for materials which provide, for example, a more refined freshorange flavor or a more refined peppermint flavor (for use in oralhygiene flavors, e.g., mouthwashes) for example, has been difficult andrelatively costly in the areas of both natural products and syntheticproducts. By the same token, the search for materials which can providea more refined patchouli aroma or a more refined "fresh air" aroma, forexample, has been difficult and relatively costly in the areas of bothnatural products and synthetic products.

Artificial flavoring agents for foodstuffs have received increasingattention in many years. For many years, such foods flavoring agentshave been preferred over natural flavoring agents at least, in part, dueto their diminished cost and their reproducible flavor qualities. Forexample, natural food flavoring agents such as extracts, concentratesand the like are often subject to wide variations due to changes inquality, and type and treatment of the raw materials. Such variationscan be reflected in the end product and result in unfavorable flavorcharacteristics in said end product. Additionally, the presence of thenatural product in the ultimate food may be undesirable because ofincreased tendency to spoil. This is particularly troublesome in foodand food uses where such products as dips, soups, chips, sausages,gravies and desserts and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavoring agents is thatthe artificial flavor to be achieved be as natural as possible. Thisgenerally proves to be a difficult task since the mechanism for flavordevelopment in many foods, medicinal products, chewing gums, toothpastesand chewing tobaccos is not completely known. This is noticable inproducts having fresh orange and peppermint flavor characteristicsparticularly.

Even more desirable are products that conserve to substitute fordifficult to obtain natural perfumery oils and at the same timesubstitute for natural flavoring ingredients in foodstuffs, chewinggums, medicinal products, toothpastes, chewing tobaccos, smokingtobaccos and smoking tobacco article components.

Oxo reaction products are well known in the art of perfumery. Thus, U.S.Letters Pat. No. 4,374,277 issued on Feb. 15, 1983, the specification ofwhich is incorporated by reference herein, describes branched chain C₁₁aldehydes and alcohols, processes for producing same by (i) firstdimerizing isoamylene (2methyl-2-butene) to form a mixture ofdiisoamylenes and (ii) reacting the resulting mixture of separatedcomponents thereof with carbon monoxide and hydrogen by means of an oxoreaction, as well as methods for augmenting or enhancing the aroma ofperfumes, colognes and perfumed articles by adding thereto aromaaugmenting or enhancing quantities of the thus produced C₁₁ branchedchain aldehydes and alcohol compositions of matter.

Furthermore, ether carboxaldehydes are well known in the art ofperfumery for augmenting or enhancing the aroma of perfume compositionsor perfumed articles. Thus, U.S. Pat. No. 4,359,390 issued on Nov. 16,1982, the specification for which is incorporated by reference hereindiscloses the use of such ether carboxaldehydes as the compound havingthe structure: ##STR7## in augmenting or enhancing the aroma of perfumecompositions, colognes and perfumed articles (e.g., perfume plastics,solid or liquid anionic, cationic, nonionic or zwitterionic detergents,fabric softener compositions or drier-added fabric softener articles.

Application for U.S. Letters Patent, Ser. No. 335,794 filed on Sept. 26,1983, the specification for which is incorporated by reference hereindiscloses 5-alkoxybicyclo[2.2.1]heptane-2-oxypropane derivatives.

The invention of Ser. No. 335,794 relates to5-alkoxybicyclo[2.2.1]heptane-2-oxypropane derivatives defined accordingto the structure: ##STR8## (wherein R represents C₁ -C₃ alkyl andwherein Z represents one of the moieties, carbinol having the structure:##STR9## or carboxaldehyde having the structure: ##STR10## and usesthereof in augmenting or enhancing the aroma of perfume compositions,colognes or perfumed articles (e.g., solid or liquid anionic, cationic,nonionic or zwitterionic detergents, fabric softener compositions,fabric softener articles, cosmetic powders, hair preparations, perfumedpolymers and the like).

In addition, U.S. Pat. No. 4,114,420 issued on Nov. 8, 1983 describesthe process for the preparation of an aldehyde ether of the generalformula: ##STR11## wherein R₁ and R₂ each, independently of the other,represent a C₁ to C₄ alkyl radical, and R₃ and R₄ each, independently ofthe other, represent a hydrogen atom or a C₁ to C₃ alkyl radical, orwherein R₁ represents a C₁ to C₄ alkyl radical, R₂ and R₃ together withthe carbon atoms to which they are attached form a 5-membered or6-membered cycloaliphatic ring, and R₄ represents a hydrogen atom or aC₁ to C₃ alkyl radical, and wherein Y represents --CH₂ --CH₂ --CH₂ -- or--CH₂ --CH(CH₃)--, which comprises contacting a compound of the generalformula: ##STR12## wherein R₁, R₂, R₃, and R₄ are as defined above, withhydrogen and carbon monoxide under hydroformylation conditions and inthe presence of a catalytic amount of a hydroformylation catalyst.

Nothing in the prior art, however, suggests the ether carbinols or ethercarboxaldehydes of our invention or the products produced according tothe processes which comprise reacting allylic ethers with carbonmonoxide and hydrogen via an oxo reaction to produce compositions ofmatter containing such ether carboxaldehydes or subsequent reductionthereof to produce the ether carbinols of our invention or theorganoleptic uses of same.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR13##

FIG. 2 is the NMR spectrum for the peak indicated by reference numerial"10" on FIG. 1 which is the GLC profile for fraction 4 of thedistillation product of the reaction product of Example II containingthe compound having the structure: ##STR14## (Conditions: Fieldstrengths: 100 MHz; solvent: CFCl₃).

FIG. 3A is the GLC profile for the crude reaction product of Example IIcontaining the compound having the structure: ##STR15##

FIG. 3B is the GLC profile for fraction 5 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR16##

FIG. 4 is the NMR spectrum for peak "50" of the GLC profile of FIG. 3Bfor the compound having the structure: ##STR17## (Conditions: Fieldstrength: 100 MHz; solvent: CFCl₃).

FIG. 5 is the GLC profile for bulked fractions 2-4 of the firstdistillation product of the reaction product of Example III containingthe compound having the structure: ##STR18##

FIG. 6 is the GLC profile for fraction 5 of the second distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR19##

FIG. 7 is the NMR spectrum for the compound having the structure:##STR20## produced according to Example III (Conditions: Field strength:100 MHz; solvent: CFCl₃).

FIG. 8 is the GLC profile for the crude reaction product of Example IVcontaining the compounds having the structures: ##STR21##

FIG. 9 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example IV containing the compound having thestructure: ##STR22##

FIG. 10 is the NMR spectrum for the compound having the structure:##STR23## produced according to Example IV (Conditions: Field strength:100 MHz; solvent: CFCl₃).

FIG. 11 is the infra-red spectrum for the compound having the structure:##STR24## produced according to Example IV.

FIG. 12 is the GLC profile of the crude reaction product of Example Vcontaining the compound having the structure: ##STR25##

FIG. 13 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example V containing the compound having thestructure: ##STR26##

FIG. 14 is the GLC profile for the crude reaction product of Example VIcontaining the compound having the structure: ##STR27##

FIG. 15 is the NMR spectrum for fraction 2 of the distillation productof the reaction product of Example VI containing the compound having thestructure: ##STR28## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 16 is the GLC profile for the crude reaction product of Example VIIcontaining the compound having the structure: ##STR29## (Conditions: SE30 column programmed at 100°-200° C. at 8° C. per minute).

FIG. 17 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example VII containing the compound havingthe structure: ##STR30##

FIG. 18 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example VIII containing the compound having thestructure: ##STR31##

FIG. 19 is the NMR spectrum for fraction 8 of the distillation productof the reaction product of Example VIII containing the compound havingthe structure: ##STR32## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG.20 is the GLC profile for the crude reaction product of Example IXcontaining the compound having the structure: ##STR33##

FIG. 21 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example IX containing the compound having thestructure: ##STR34## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 22A is the GLC profile for the crude reaction product of Example Xcontaining the compound having the structure: ##STR35##

FIG. 22B is the NMR spectrum for the compound having the structure:##STR36## produced according to Example X (Conditions: Solvent; CFCl₃ :Field strength: 100 MHz).

FIG. 23 represents a cut-away side elevation view of apparatus used informing perfumed polymers which contain embedded therein at least one ofthe ether carbinols of our invention.

FIG. 24 is a front view of the apparatus of FIG. 23 looking in thedirection of the arrows.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR37##

The peak indicated by the Reference 10 is the peak for the compoundhaving the structure: ##STR38##

FIG. 3A is the GLC profile for the crude reaction product of Example IIcontaining the compounds having the structures: ##STR39## The peakindicated by Reference 30 is the peak for the compound having thestructure: ##STR40## The peak indicated by Reference 31 is the peak forthe compound having the structure: ##STR41##

FIG. 3B is the GLC profile for fraction 5 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR42## The peak indicated by Reference 50 is the peak forthe compound having the structure: ##STR43##

FIG. 8 is the GLC profile for the crude reaction product of example IVcontaining the compounds having the structures: ##STR44## The peakindicated by Reference 80 is the peak for the compound having thestructure: ##STR45## The peak indicated by Reference 81 is the peak forthe compound having the structure: ##STR46## The peak indicated byReference 82 is the peak for the compound having the structure:##STR47## The peak indicated by Reference 83 is the peak for thecompound having the structure: ##STR48##

FIG. 9 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example IV containing the compound having thestructure: ##STR49## as well as the compound having the structure:##STR50## The peak indicated by Reference 91 is the peak for thecompound having the structure: ##STR51## The peak indicated by Reference92 is the peak for the compound having the structure: ##STR52##

Referring to FIGS. 23 and 24, there is provided a process for formingscented polymer elements (wherein the polymer may be a thermoplasticpolymer such as low density polyethylene or polypropylene or copolymersof ethylene and vinyl acetate or mixtures of polymers and copolymerssuch as copolymers of ethylene and vinyl acetate and polyethylene) suchas pellets useful in the formation of plastic particles useful infabricating certain articles which may be perfumed. This processcomprises heating the polymer or mixture of polymers to the meltingpoint of said polymer or mixture of polymers, e.g., 250° C. in the caseof low density polyethylene. The lower most portion of the container ismaintained at a slightly lower temperature and the material in thecontainer is taken off at such location for delivery through theconduit. Thus, referring to FIGS. 23 and 24, in particular, theapparatus used in producing such elements comprises a device for formingthe polymer containing perfume, e.g., polyethylene orpolyethylene-polyvinyl acetate or mixtures of same or polypropylene,which comprises a vat or container 212 into which the polymer takenalone or in admixture with other copolymers and the perfuming substancewhich is at least one of the ether carbinols or ether carboxaldehydes ofour invention or mixtures of ether carbinols and ether carboxaldehydesand other compatible perfumes is placed. The container is closed bymeans of an air-tight lid 228 and clamped to the container by bolts 265.A stirrer 273 traverses the lid or cover 228 in an air-tight manner andis rotatable in a suitable manner. A surrounding cylinder 212A havingheated coils which are supplied with electric current through cable 214from a rheostat or control 216 is operated to maintain the temperatureinside the container 212 such that the polymer in the container will bemaintained in the molten or liquid state. It has been found advantageousto employ polymers at such a temperature that the viscosity will be inthe range of 90-100 sayboldt seconds. The heater 218 is operated tomaintain the upper portion of the container 212 within a temperaturerange of, for example, 220°-270° C. in the case of low densitypolyethylene. The bottom portion of the container 212 is heated by meansof heating coils 212A regulated through the control 220 connectedthereto through a connecting wire 222 to maintain the lower portion ofthe container 212 within a temperature range of 220°-270° C.

Thus, the polymer or mixture of polymers added to the container 212 isheated from 10-12 hours, whereafter the perfume composition or perfumematerial which contains one or more of the ether carbinols and/or ethercarboxaldehydes of our invention is quickly added to the melt.Generally, about 10-45 percent by weight of the resulting mixture of theperfumery substance is added to the polymer.

After the perfume material is added to the container 212, the mixture isstirred for a few minutes, for example, 5-15 minutes and maintainedwithin the temperature ranges indicated previously by the heating coil212A. The controls 216 and 220 are connected through cables 224 and 226to a suitable supply of electric current for supplying the power forheating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer in intimate admixture with one or moreof the ether carbinols and/or ether carboxaldehydes of our invention ormixture of perfume substances and one or more of the ether carbinolsand/or ether carboxaldehydes of our invention, will continuously dropthrough the orifices 234 downwardly from the conduit 232. During thistime, the temperature of the polymer intimately admixed with theperfumery substance in the container 212 is accurately controlled sothat a temperature in the range of from about 240°-250° C., for example,(in the case of low density polyethylene) will exist in the conduit 232.The regulation of the temperature through the controls 216 and 220 isessential in order to insure temperature balance to provide for thecontinuous dripping or dropping of molten polymer intimately admixedwith the perfume substance which is all of or which contains one or moreof the ether carbinols and/or ether carboxaldehydes of our invention,through the orifices 234 at a rate which will insure the formation ofdroplets 236 which will fall downwardly onto a moving conveyor belt 238caused to run between conveyor wheels 240 and 242 beneath the conduit232.

When the droplets 236 fall onto the conveyor 238, they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 250 which is advantageously filled with water orsome other suitable cooling liquid to insure the rapid cooling of eachof the pellets 244. The pellets 244 are then collected from thecontainer 250 and utilized for the formation of other functionalproducts, e.g., garbage bags and the like.

THE INVENTION

The present invention provides ether carbinols defined according to thegeneric structure: ##STR53## wherein X₁ represents a moiety selectedfrom the group consisting of: ##STR54## and wherein Y₁ represents C₄ orC₅ alkylene; C₄ or C₅ alkenylene or C₄ or C₅ alkynylene as well as ethercarboxaldehydes defined according to one of the following twostructures: ##STR55## The present invention also provides processes forpreparing such compounds by means of carrying out an oxo reaction on anappropriate allyl ether using carbon monoxide and hydrogen and eitherisolating the resulting carboxaldehyde or further reducing the resultingether carboxaldehyde to form the appropriate ether carbinol; or reactingcamphene with either an alkylene diol, an alkenylene diol or analkynylene diol in the presence of an appropriate catalyst to form anorbornyloxycarbinol. More specifically, an allyl ether definedaccording to the formula: ##STR56## is reacted with a mixture of carbonmonoxide and hydrogen using an oxo reaction catalyst whereby a mixtureof aldehydes is formed defined according to the structure: ##STR57##according to the reaction: ##STR58## wherein p and q each represent 0 or1 with the proviso that when p is 0 q is 1 and that when p is 1 q is 0and wherein R represents hydrogen or methyl. The resulting ethercarboxaldehyde mixture defined according to the structure: ##STR59## maybe used "as-is" for its organoleptic properties or may be furtherreduced with an appropriate reducing agent to form the ether carbinoldefined according to the structure: ##STR60## on the other hand, anotherprocess of our invention involves the reaction of camphene definedaccording to the structure: ##STR61## with an alkylene diol, analkenylene diol or an alkynylene diol defined according to thestructure: ##STR62## in order to form a norbornyloxycarbinol definedaccording to the structure: ##STR63## according to the reaction: whereinY₁ represents C₄ or C₅ alkylene; C₄ or C₅ alkenylene; or C₄ or C₅alkynylene.

The present invention also provides products produced according to suchprocesses. The resulting compounds, ether carboxaldehydes of ourinvention or ether carbinols of our invention, produced according to theprocesses of our invention are capable of augmenting or enhancing thearoma and/or taste of consumable materials including foodstuffs, chewinggums, toothpastes, medicinal products, chewing tobaccos, perfumes,perfumed articles, colognes, smoking tobaccos and smoking tobaccoarticles.

Thus, the ether carbinols and ether carboxaldehydes of our inventionaugment or enhance the ozoney, fresh air dried clothing-like, green,orange, nutty, woody, minty, patchouli, incense-like, oniony, garlic,lavender-like, herbaceous, leafy, pepper, spicy, camphoraceous, sweet,fruity and chamomile-like aromas and patchouli-like, cedarwood-like,oniony, animalic sweaty, herbaceous, peppery, olibanum, diffusive amber,rosey and caramellic undertones of perfumed compositions, colognes andperfumed articles (including soaps, anionic, cationic, nonionic orzwitterionic detergents, fabric softener compositions, fabric softenerarticles, optical brightner compositions, perfumed polymers, hairpreparations and the like, thus fulfilling a need in the field ofperfumery as well as detergent, cologne, fabric softener and cosmeticmanufacture.

In the area of foodstuffs, chewing gums, toothpastes, medicinal productsand chewing tobaccos, as well as flavoring compositions therefor, theether carboxaldehydes and/or ether carbinols of our invention producedaccording to the processes of our invention in part augment or enhancegreen, fresh orange, patchouli, oriental, incense-like, musky,sandalwood, walnut-like, onion, garlic, floral and fruity aroma andtaste nuances, thereby creating valuable aroma and taste nuances usefulfor oral hygiene, peppermint, fresh orange, walnut, onion, garlic andfruit flavored foodstuffs.

In smoking tobacco, smoking tobacco flavoring compositions, substitutesmoking tobacco and substitute tobacco flavoring compositions, the ethercarboxaldehydes and/or ether carbinols of our invention producedaccording to the processes of our invention in part augment and enhancewoody, incense, oriental and patchouli aroma and taste nuances bothprior to and on smoking in the main stream and in the side stream.

The ether carbinols of our invention defined according to the structure:##STR64## wherein X₁ represents a structure selected from the groupconsisting of: ##STR65## and wherein Y represents C₄ -C₅ alkylene, C₄-C₅ alkenylene and C₄ -C₅ alkynylene may be prepared by means of firstreacting allyl ethers defined according to the structure: ##STR66## withcarbon monoxide and hydrogen thereby carrying out a "oxo" reaction. Theallyl ethers defined according to the structure: ##STR67## may beprepared by means of any standard ether synthesis, e.g., a "Williamson"synthesis or a synthesis as set forth in U.S. Pat. No. 4,163,068 issuedon July 31, 1979, the specification for which is incorporated byreference herein. Thus, the ethers so useful in our invention may beformed by reacting an alcohol with another alcohol, for example, anallylic alcohol in the presence of an acid catalyst such as para toluenesulphonic acid at reflux conditions. The reaction mass is refluxed for aperiod of from two hours up to ten hours, after which period of time thereaction product is separated from the reaction mass by distillation.

The ethers so useful in practicing our invention may also be formed byreacting the corresponding alcohol with an appropriate allylic halide orother organic halide as the case may be. This reaction is carried outunder the influence of base comprising the step of placing the reactantsfor the process and the base, respectively, in tow immiscible phases; anorganic phase and either (i) an aqueous base phase or (ii) a solid basephase with the reactants being located substantially entirely in thefirst mentioned organic phase and the base being located substantiallyentirely in the second mentioned phase; and adding to the two phasesystem a "phase transfer agent" which may be one or more of severalorganic quaternary ammonium salts.

Specific examples of "phase transfer agents" useful in our invention areas follows:

Tricapryl methyl ammonium chloride;

Cetyl trimethyl ammonium bromide; and

Benzyl trimethyl ammonium hydroxide.

In general, the "phase transfer agents" most preferred have the genericformula: ##STR68## wherein at least one of R₁ ', R₂ ', R₃ ' and R₄ ' isC₆ -C₁₄ aryl, C₆ -C₁₀ aralkyl, C₆ -C₂₀ alkyl, C₆ -C₁₄ aralkyl and C₆-C₂₀ alkenyl, and the other of R₂ ', R₃ ' and R₄ ' is alkyl such asmethyl, ethyl, n-propyl, i-propyl, 1-butyl, 1-methyl-2-propyl, 1-pentyland 1-octyl and Z- is an anion such as chloride, bromide and hydroxide.

This aspect of the process is carried out in an inexpensive solventwhich is inert to the reaction system such as toluene, benzene,o-xylene, m-xylene, p-xylene, ethyl benzene, n-hexane, cyclohexane,methylene dichloride and o-dichlorobenzene.

This aspect of the process is carried out at a temperature in the rangeof from about 10° C. up to about 150° C. with a temperature range of30°-120° C. being preferred. The reaction time is inversely proportionalto the reaction temperature, with lower reaction temperatures givingrise to greater reaction times; and, accordingly, the reaction timeranges from about 30 minutes up to about 10 hours.

In this aspect of the process, the mole ratio of alcohol reactant toorganic halide (e.g., allylic halide) is in the range of from 0.5:1.5 upto about 1.5:0.5 with a preferred ratio of alcohol to organic halide(e.g., allylic halide) being from about 1:1 up to about 1:1.2.

The mole ratio of base to alcohol in the reaction mass may be in therange of from about 0.75:1 up to about 1.5:1 with a preferred mole ratioof base:alcohol being from about 1:1 up to about 1.2:1.

The quantity of "phase transfer agent" in the reaction mass based on theamount of alcohol in the reaction mass may vary from 0.5 grams per moleof alcohol up to 25 grams of "phase transfer agent" per mole of alcoholwith a preferred concentration of "phase transfer agent" being in therange of from about 2.5 up to about 7.5 grams of "phase transfer agent"per mole of alcohol.

This aspect of the process is preferably carried out at atmosphericpressure since that is the most convenient condition. However, lower orhigher pressures can be used without detrimentally affecting theultimate yield of desired product. The particular based used in thereaction is not critical, but, preferred are sodium hydroxide andpotassium hydroxide.

The individual ethers which are reactants for our invention in the oxoprocess described, infra, can be obtained in pure form or insubstantially pure form by conventional purification techniques. Thus,the products can be purified and/or isolated by means of distillation,extraction, crystallization, preparative chromatographic techniques andthe like. It has been found desirable to purify the ethers by fractionaldistillation in vacuo.

The thus-formed ethers having the structure: ##STR69## wherein Rrepresents methyl or ethyl and X₁ is as defined, supra, are then reactedwith a mixture of carbon monoxide and hydrogen using a particular rangeof temperatures and partial pressures of hydrogen and carbon monoxideover one of several alternative "oxo" type reaction catalysts over aperiod of various residence times.

Thus, the oxo reaction is carried out thusly: t,0381

wherein X₁, R, p and q are defined, supra, with the production of asmall amount of alcohol defined according to the structure: ##STR70##The reaction is carried out at temperatures of between 150° C. and 300°C.; at pressures of between 20 and 250 atmospheres; with the ratio ofpartial pressure of carbon monoxide:hydrogen being from 0.1:1 up to1:0.1. Any oxo type reaction catalyst may be used, but most preferably,the catalyst to yield the best perfume and flavor mixtures are asfollows:

Dicobalt octacarbonyl;

Cobalt octanoate;

Palladium chloride;

Rhodium trichloride;

Iron pentacarbonyl;

Nickel tetracarbonyl;

Polymer-bonded rhodium catalyst (e.g., rhodium bonded on a polystyrenesubstrate);

Tris-triphenyl phosphine rhodium-1-chloride;

Rhodium Aceto acetate dicarbonyl;

Rhodium Aceto acetate/triphenyl phosphine mixture.

The reaction time may vary from about two hours up to about 30 hours;and the reaction time is a function of the temperature and pressure ofreaction; and the desired ratio of aldehyde: alcohol reaction product.Insofar as the instant invention is concerned, a high ratio ofalcohol:aldehyde reaction product will be created by high temperaturehigh pressure and a long period of time whereas a high ratio ofaldehyde:alcohol will be created as a result of low temperature lowpressure and short period of time.

At the end of the reaction, the reaction product is separated from thecatalyst and unreacted materials by standard "work-up" means if desired;e.g., neutralization of catalyst; followed by extraction and fractionaldistillation; usually an initial fractional distillation by means ofdistillation through a 2-4 plate or stone packed column; followed by amore careful fractionation of the bulked center-cut fractions on, forexample, a spinning band column or multiplate (14-50 plate)fractionation column.

The resultant aldehyde reaction product may then be reduced by means ofusing specific reducing agents according to the reaction: ##STR71##wherein X₁, R, p and q are defined, supra. The reduction reaction iscarried out at a temperature in the range of from about 60° C. up toabout 100° C. at from about one atmosphere up to about 10 atmospheresbut preferably at reflux conditions for a period of time of betweenabout one and 10 hours. The reaction takes place in the presence of asolvent which is inert to the reactants and the reaction product, suchas, anhydrous isopropyl alcohol. Such solvent must be capable of beingretained during the course of the reaction and not being so volatile asto boil off during the reaction. The reducing agent may be any standardaldehyde-alcohol reducing agent but preferable reducing agents are alkylmetal borohydrides, for example, sodium borohydrides, potassiumborohydrides and lithium borohydrides. Other reducing agents that can beused are lithium aluminum hydride and alumininum isopropoxide andpotassium isobutoxide. At the end of the reaction the reaction productwhich is the ether carbinol of our invention may be isolated from thereaction mass by standard isolation means, e.g., fractionalcrystallization, fractional distillation and commercial liquidchromotography procedures.

In addition, nornyloxocarbinols defined according to the genericstructure: ##STR72## wherein Y₁ represents alkylenyl, alkenylenyl andalkynylenyl having from four up to five carbon atoms may be prepared byreacting camphene with a diol defined according to the structure:##STR73## according to the reaction:

This reaction takes place in the presence of a catalyst which is a Lewisacid, for example, boron trifluoride etherate at temperatures in therange of from about 60° C. up to about 100° C. and at pressures in therange of from about 1 atmosphere up to about 10 atmospheres. Preferably,the reaction takes place at 80° C. at atmospheric pressure and at refluxcondition. The reaction time may vary from about two hours up to about20 hours depending upon the temperature of reaction. Higher temperaturesof reaction gives rise to lower times of reaction and lower temperaturesof reaction require higher times of reaction but a better overall yield.The mole ratio of diol having the structure: ##STR74## to camphene mayvary from about 1:2 up to about 3:1 with a mole ratio of diol:campheneof about 2:1 being preferred. At the end of the reaction the reactionmass is neutralized and the reaction product defined according to thegeneric structure: is purified for organoleptic uses as by means offractional distillation.

Examples of ether carbinols and ether carboxaldehydes which are usefulin the practice of our invention and their organoleptic properties areset forth in the following Tables I (Ether Carbinols) and II (EtherCarboxaldehydes):

                                      TABLE I                                     __________________________________________________________________________                                                         Tobacco Flavor           Ether Carbinol      Perfumery Evaluation                                                                            Food Flavor Evaluation                                                                       Evaluation               __________________________________________________________________________     ##STR75##          Nutty, woody, ozoney, fresh air dried cloth,                                  green-orange aroma profile.                                                                     A green aroma and taste with fresh                                            orange nuances.                          ##STR76##          A minty patchouli aroma with patchouli                                                          A patchouli, oriental, incense,                                               musky and sandal- wood aroma and                                              taste profile at 5 ppm causing it                                             to be good for oral hygiene and                                               peppermint flavor.                       ##STR77##          An incense aroma with  cedarwood undertones.                                                    A walnut-like flavor.                                                                        A woody incense                                                               oriental and                                                                  patchouli aroma and                                                           taste profile both                                                            prior to and on                                                               smoking in the main-                                                          tream and the side-                                                           stream.                   ##STR78##          An onion, garlic and lavender aroma profile with                              oniony animalic and sweaty undertones.                                                          An onion garlic aroma and taste                                               profile.                                 ##STR79##          A camphoraceous, woody lavender and spicy and floral                          aroma with patchouli and rosy undertones.                                                       A walnut-like flavor.                   __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________                                                  Tobacco Flavor                  Ether Aldehyde    Perfumery Evaluation                                                                          Food Flavor Evaluation                                                                    Evaluation                      __________________________________________________________________________     ##STR80##        A herbaceous, strong green leafy, pepper and spicy                            aroma profile with herbaceous peppery olibanum and                            diffusive amber undertones.                                                                   A floral flavor profile.                    prepared according to Example VIII                                             ##STR81##        A herbaceous sweet fruity chamomile-like aroma with                           caramellic undertones.                                                                        A fruity flavor.                                                                          A fruity aroma and taste                                                      profile both prior to and                                                     on smoking in the main-                                                       stream and the side-                                                          stream.                         prepared according to Example X                                               __________________________________________________________________________

When one or more of the ether carboxaldehydes and/or ether carbinols andreaction products containing same of our invention is used as a foodflavor adjuvant, the nature of the co-ingredients included with said oneor more ether carboxaldehydes and/or ether carbinols in formulating theproduct composition will also serve to alter the organolepticcharacteristics of the ultimate foodstuffs treated therewith. As usedherein, in regard to flavors, the term "alter" in its various formsmeans "supplying or imparting flavor character or notes to otherwisebland relatively tasteless substance or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste".

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not have nutritionalvalue. Thus, foodstuffs include soaps, convenience foods, beverages,dairy products, candies, fruits, cerals, soft drinks, snacks and thelike.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be "ingestibly" acceptable and thus non-toxic orotherwise non-deleterious, nothing particularly critical resides inselection thereof. Accordingly, such materials which may in general becharacterized as flavoring adjuvants or vehicles comprise broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3 tertiarybutyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like,and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agaragar;carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatine; proteinaceous materials; lipids;carbohydrates; starches pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup solids and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypocchlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like,colorants, e.g., carminic acid, cochineal, tumeric and curcumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers; anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes, yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, butyric acid, caproic acid, caprylic acid, formic acid,2-hexenoic acid, 3-hexenoic acid, isobutyric acid, isovaleric acid,propionic acid and valeric acid; ketones and aldehydes, e.g.,acetaldehyde, acetone, acetyl methyl carbinol, acrolein, diacetyl, β,β-dimethylacrolein, hexanal, 2-hexenal, cis-3-hexenal,4(p-hydroxyphenyl)-2-butanone, α-ionone, β-ionone, and 2-pentenal;alcohols, such as 1-butanol, trans-2-buten-1-ol, ethanol, gernaiol,1-hexanol, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentalol,1-penten-3-ol; esters, such as butyl acetate, ethyl acetate, ethylbutyrate, ethyl crotonate, ethyl propionate, 2-hexenyl acetate,2-hexenyl butyrate, hexyl acetate, hexyl butyrate, isoamyl acetate,isopropyl butyrate, methyl butyrate, methyl caproate, methyl caprylate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutylcinnamate, and terpenyl acetate; essential oils such as jasmineabsolute, rose absolute, orris absolute, lemon essential oil andvanilla; lactones; sulfides, e.g., methyl sulfide and other materialssuch as maltol and citral as well as natural orange oil, naturalpeppermint oil, strawberry juice concentrate and the like.

The specific flavoring adjuvants selected for use may be either solid orliquid, depending upon the desired physical form of the ultimateproduct, i.e., foodstuff, whether simulated or natural and should, inany event, be capable of providing an environment in which the one ormore ether carboxaldehydes and/or ether carbinols of our invention canbe dispersed or admixed to provide a homogeneous medium. In addition,the selection of one or more adjuvants as well as the quantitiesthereof, will depend upon the precise organoleptic natural orangecharacter, natural orange juice character, natural peppermint characteror natural walnut character desired in the finished product. Thus, inthe case of flavoring compositions, ingredients selection will vary inaccordance with the foodstuffs to which the flavor and aroma are to beimparted. In contradistinction, in the preparation of solid products,e.g., simulated foodstuffs, ingredients capable of providing normallysolid compositions should be selected, such as various cellulosederivatives.

As will be appreciated by those skilled in the art, the amount of one ormore ether carboxaldehydes and/or ether carbinols of our inventionemployed in a particular instance can vary over a relatively wide rangewhereby its desired organoleptic effects (having reference to the natureof the product) are achieved. All parts and percentages given herein areby weight unless otherwise specified. Thus, correspondingly greateramounts would be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for the purposes of enhancingthe composition merely deficient in natural flavor or aroma. Thus, theprimary requirement is that amount which is effective, i.e., sufficientto alter the organoleptic characteristics of the parent composition,whether foodstuff, per se, or flavoring composition. Thus, the use ofinsufficient quantities of one or more ether carboxaldehydes and/orether carbinols of our invention will, of course, substantially vitiateany possibility of obtaining the desired results while excess quantitiesprove needlessly costly and in extreme cases, may disrupt theflavor/aroma balance, thus proving self-defeating. Accordingly, theterminology "effect amount" and "sufficient amount" is to be accorded asignificance in the context of the present invention consistent with theobtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, it has been foundthat quantities of one or more ether carboxaldehydes and/or ethercarbinols of our invention ranging from a small but effective amount,e.g., 0.02 parts per million up to about 100 parts per million by weightbased on total composition are suitable. Concentrations in excess of themaximum quantity stated are not normally recommended since they fail toprovide commensurate enhancement of organoleptic properties. In thosecases wherein the one or more ether carboxaldehydes and/or ethercarbinols of our invention is added to the foodstuff as an integralcomponent of the flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective ether carboxaldehyde and/or ether carbinolconcentration in the foodstuff product.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitjuices and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by admixing one or more ether carboxaldehydesand/or ether carbinols of our invention with, for example, gum arabic,gum tragacanth, guar gum and the like and thereafter spray-drying theresultant mixture whereby to obtain the particulate solid product.Prepared flavor mixes in powder form, e.g., an orange-flavored powder ora peppermint-flavored powder are obtained by mixing dry solidcomponents, e.g., starch, sugar and the like and one or more ethercarboxaldehydes and/or ether carbinols in a dry blender until therequisite degree of uniformity is achieved.

It is presently preferred to combine one or more of the ethercarboxaldehydes and/or ether carbinols of our invention with thefollowing adjuvants:

Parahydroxybenzyl acetone;

Vanillin;

Maltol;

β-Ionone;

β-Ionone;

Isobutyl acetate;

Ethyl butyrate;

Dimethyl sulfide;

Acetic acid;

Acetaldehyde;

4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone;

4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone;

2-(4-hydroxy-4-methylpentyl)norbornadiene produced according to ExampleI of U.S. Pat. No. 3,911,028;

β-Damascone(1-crotonyl-2,6,6-trimethylcyclohex-1-ene);

β-Damascenone(1-crotonyl-2,6,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral(2,6,6-trimethylcyclohex-1-ene carboxaldehyde)

Isoamyl butyrate;

Cis-3-hexenol-1;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene);

Cis-2-3-methyl pentenoic acid;

Ethyl-2-methyl-3-pentenoate;

Isobutyl-cis-2-methyl-3-pentenoate;

2-Ethylidene-3-pentenal;

Orange oil;

Lemon oil;

Peppermint oil;

Strawberry juice extract;

Raspberry juice extract;

Cranberry juice extract;

Mango extract;

Pickled mango extract; and

Pulverized walnuts.

One or more ether carboxaldehyde derivatives and/or ether carbinolderivatives prepared in accordance with the processes of our inventionand one or more auxiliary perfume ingredients, including, for example,alcohols other than those of our invention; aldehydes other than thoseof our invention; ketones; topenic hydrocarbons; nitriles; esters;lactones; natural essential oils; and snythetic essential oils may beadmixed so that the combined odors of the individual components producea pleasant and desired fragrance, particularly and preferably in thegreen, organe, ozoney, patchouli, incense, sandalwood, musk, cedarwood,minty, lavender, herbaceous, woody and chamomile fragrances. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation and substances which retard evaporation; and (d)topnotes which are usually low boiling, fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the ether carboxaldehyde derivatives and/or ether carbinolderivatives prepared in accordance with the processes of our inventioncan be used to alter, modify or enhance the aroma characteristics of aperfume composition, for example, by utilizing or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of one or more ether carboxaldehyde derivatives and/or ethercarbinol derivatives prepared in accordance with the processes of ourinvention which will be effective in perfume composition as well as inperfumed articles (e.g., anionic, nonionic, cationic and zwitterionicsolid or liquid detergents, soaps, fabric softener compositions,drier-added fabric softener articles, optical brightener compositions,perfumed polymers and textile sizing agents) and colognes depends onmany factors, including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.01% of one or more of the ether carboxaldehydederivatives and/or ether carbinol derivatives of our invention preparedin accordance with the processes of our invention and less than 50% ofone or more of the ether carboxaldehyde derivatives and/or ethercarbinol derivatives prepared in accordance with the processes of ourinvention or even less (e.g., 0.005%) can be used to impart, augment orenhance ozoney, fresh air dried cloth-like, green, orange, nutty, woody,minty, patchouli-like, incense-like, oniony, garlic, lavender-like,herbaceous, leafy, pepper-like, spicy, camphoraceous, woody, fruity andchamomile-like aroma nuances with patchouli-like, cedarwood, oniony,animalic sweaty, herbaceous, peppery, olibanum, diffusive amber, roseyand caramellic undertones to soaps, cosmetics, solid or liquid anionic,nonionic, cationic and zwitterionic detergents, fabric softenercompositions, fabric softener articles, optical brightener compositions,textile sizing compositions, perfumed polymers or other products. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations, of course, nature of the end product, theeffect desired on the finished product and the particular fragrancesought.

One or more ether carboxaldehyde derivatives and/or ether carbinolderivatives prepared in accordance with the processes of our inventionare useful (taken alone or together with other ingredients in perfumecompositions) as (an) olfactory component (s) in detergents and soaps,space odorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as, talcs, dusting powders, face powders, and perfumedpolymers and articles of manufacture produced from said perfumedpolymers, e.g., garbage bags, children's toys and the like. When used as(an) olfactory component (s) as little as 0.2% of one or more of theether carboxaldehyde derivatives and/or ether carbinol derivativesprepared in accordance with the processes of our invention will sufficeto impart, augment or enhance intense ozoney, fresh air driedcloth-like, green, orange, nutty, woody, minty, patchouli-like,incense-like, oniony, garlic-like, lavender-like, herbaceous, leafy,pepper, spicy, camphoraceous, woody, sweety fruit and chamolime-likearoma nuances with patchouli-like, cedarwood-like, oniony, animalicsweaty, herbaceous, peppery olibanum, diffusive amber, rosey andcaramellic undertones to floral, piney, lavender, spicy and patchouliformulations. Generally, no more than 6% of one or more of the ethercarboxaldehyde derivatives and/or ether carbinol derivatives of ourinvention based on the ultimate end product as required in the perfumedarticle composition. Accordingly, the range of ether carboxaldehydesand/or ether carbinols in the perfumed article is from about 0.2% byweight of the ether carboxaldehyde and/or ether carbinol up to about 6%by weight of the ether carboxaldehyde and/or ether carbinol based on thetotal weight of the perfumed article.

In addition, the perfumed composition or fragrance composition of ourinvention can contain a vehicle or carrier for one or more of the ethercarboxaldehyde derivatives and/or ether carbinol derivatives prepared inaccordance with the processes of our invention. The vehicle can be aliquid, such as, a non-toxic alcohol, e.g., ethyl alcohol, a non-toxicgylcol, e.g., propylene glycol or the like. The carrier can also be anabsorbant solid, such as, gum (e.g., gum arabic or gum orzentane) orcomponents for incapsulating the composition (such as, gelatin as bycoacervation) or such as, urea formaldehyde polymer forming a capsuleshell around a liquid perfumed center.

Our Invention also relates to the utilization of controlled releasedtechnology for the controlled release of perfumes into gaseousenvironments from polymers such as mixtures of epsilon polycaprolactonepolymers and polyethylene which polyepsilon caprolactone polymers aredefined according to at least one of the structures: ##STR82## wherein"n" is from about 50 up to about 1,200 with the proviso that the average"n" in the system varies from about 150 up to about 700 according to themathematical statement:

[700 ≧ n≧ 150]

with the term n

being the average number of repeating monomeric units for the epsilonpolycaprolactone polymer. The perfumed material's release rate from suchpolymer mixture is close to "zero order". As a general rule, the releaserate in a polymeric matrix is proportional to t^(-1/2) until about 60%of the functional fluid is released from the polymeric matrix. Therelease rate thereafter is related exponentially to time as a generalrule according to the equation: ##EQU1## wherein k₁ and k₂ areconstants. According to Kydonieus, "Controlled ReleaseTechnologies:Methods, Theory, and Applications" (cited, supra) theamount of perfume composition released is proportional to time as longas the concentration of perfume material present, e.g., the ethercarboxaldehydes and/or ether carbinols of our invention is higher thanthe solubility of the agent in the matrix. Thus, such dispersed systemsare similar to the dissolved systems except that instead of a decreasedrelease rate after 60% of the perfume material has been emitted, therelationship holds almost over the complete release curve. Kydonieusfurther states, that if one assumes that the release of functional fluidby diffusion is negligible in monolithic erodible systems, the speed oferosion will control the release rate and release by erosion by asurface-area-dependent phenomenon, the release being constant (zeroorder) as long as the surface area does not change during the erosionprocess. This is the case with the polymers containing the ethercarboxaldehydes and/or ether carbinols of our invention.

The polyepsilon caprolactone polymers useful in practicing our inventionare more specifically described in the brochure of the Union CarbideCorporation, 270 Park Avenue, New York, N.Y. 10017, entitled "NEWPOLYCAPROLACTONE THERMOPLASTIC POLYMERS PCL-300 AND PCL-700". Thesepolyepsilon caprolactone polymers are composed of a repeating sequenceof non-polar methylene groups and relatively polar ester groups. Theaverage number of repeating monomeric units varies between 150 and 700depending on the particular "PCL" number. Thus, regarding PCL-300 theaverage number of repeating monomeric units is about 300. RegardingPCL-700, the average number of repeating monomeric units is 700.

The polyepsilon caprolactone homopolymers which are ultimately taken inadmixture with such materials as polyethylene useful in the practice ofour invention may also be stabilized using stabilizers as defined inU.S. Pat. No. 4,360,682 issued on Nov. 23, 1982, the specification forwhich is incorporated herein by reference. The stabilizing materialswhich stabilize the polyepsilon caprolactone useful in conjunction withour invention against discoloration are dihydroxybenzenes suchhydroquinone or compounds having the formula: ##STR83## in which R₁ isalkyl of from 1 to 8 carbon atoms, and R₂ is hydrogen or alkyl of 1 to 8carbon atoms. It is preferable to have such stabilizer in thepolyepsilon caprolactone homopolymer in an amount of from about 100 to500 ppm. Such stabilizers do not interfere with the functional fluidsdissolved and/or absorbed into the polymeric matrix.

The method of incorporating the ether carboxaldehydes and/or ethercarbinols of our invention or perfume compositions containing same intothe polymers may be according to the techniques of U.S. Pat. No.3,505,432 issued on Apr. 7, 1970 (the specification for which isincorporated by reference herein) or U.S. Pat. No. 4,247,498 issued onJan. 27, 1981, the disclosure of which is incorporated by referenceherein.

Thus, for example, a first amount of liquid polyethylenepolyepsiloncaprolactone polymer mixture (50:50) is mixed with one of the ethercarboxaldehydes and/or ether carbinols of our invention. Drops areformed from the mixture and the drops are solidified. The solidifieddrops are then melted, if desired, with a second amount of unscented lowdensity polyethylene, for example, or polypropylene, for example.Usually, but not necessarily, the second amount of polymer is largerthan the first amount. The resulting mixture thus obtained, issolidified subsequent to or prior to ultimate casting into a utilitarianshape.

Thus, in accordance with one aspect of our invention, the imparting ofscent is effected in two stages. In a first stage, a 50:50(weight:weight) polyepsilon caprolactone, e.g., PCL-700: polyethylene inmolten form is admixed with a high percentage of one of the ethercarboxaldehydes and/or ether carbinols of our invention and the mixtureis solidified in the form of pellets or beads. These pellets or beadsthus contain a high percentage of ether carboxaldehydes and/or ethercarbinols (e.g., up to 45% by weight of the entire mixture) and may beused as "master pellets" which thereafter, in a second stage, ifdesired, may be admixed and liquified with additional polymers such asadditional polyethylene or mixtures of polyethylene and polyepsiloncaprolactone in an unscented state, or unscented polypropylene. Inaddition, additional polymers or copolymers may be used, for example,copolymers specified and described in U.K. Patent Specification No.1,589,201 published on May 7, 1981, the specification for which isincorporated by reference herein.

In accordance with the present invention at least one of the ethercarboxaldehydes and/or ether carbinols of our invention is added to thepolymer in a large closed container or drum which is maintained undercontrolled temperature conditions while the polymer in a meltedcondition is mixed with at least one of the ether carboxaldehydes and/orether carbinols under agitation.

In order that the perfume be added uniformly to the polymer, thetemperature of the melt is constantly controlled during the process. Thepolymer-perfume mixture is then directed through an elongated conduit orpipe element having a plurality of orifices adjacent to the lower mostportion thereof. The polymer enriched by at least one of the ethercarboxaldehydes and/or ether carbinols of our invention is permitted todrip through the orifices onto a continuously moving, cooled conveyorupon which the polymer containing at least one of the ethercarboxaldehydes and/or ether carbinols of our invention solidifies intosmall size pellets with the perfume imprisoned therein. The apparatususeful in conjunction with this process, advantageously includes aconveyor of a material which will not adhere to the polymer whichcontains at least one of the ether carboxaldehydes and/or ethercarbinols of our invention.

In order that the droplets form into uniform pellets or beads, theconveyor is continuously washed with a liquid, such as water to maintainthe surface relatively cool. The pellets are delivered by the conveyorinto a container and packaged for shipment.

Furthermore, one or more of the ether carboxaldehydes and/or ethercarbinols of our invention prepared in accordance with the processes ofour invention are capable of supplying and/or potentiating certainflavor and aroma notes usually lacking in many smoking tobacco flavorsand substitute tobacco flavors heretofore provided.

As used herein in regard to smoking tobacco flavors, the terms "alter"and "modify", in their various forms, mean "supplying or impartingflavor character or note to otherwise bland smoking tobacco, smokingtobacco substitutes, or smoking tobacco flavor formulations oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of smoking tobacco or a smoking tobacco substitute or asmoking tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired woody, green, herbaceous and spicy aroma and tastenuances prior to and on smoking in both the main stream and in the sidestream are created or enhanced and may be readily controlled andmaintained at the desired uniform level regardless of variations in thetobacco components of the blend.

This invention further provides various improved smoking tobaccoadditives and methods, whereby, various woody, incense-like, orientaland patchouli nuances are imparted (on smoking in the main stream and inthe side stream) to smoking tobacco products and may be readily variedand controlled to produce the desired uniformed flavor characteristics,particularly, insofar as "oriental" like tobacco characteristics areconcerned.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone or more of the ether carboxaldehydes and/or ether carbinols preparedin accordance with the processes of our invention.

In addition to one or more of the ether carboxaldehydes and/or ethercarbinols prepared in accordance with the processes of our invention,other flavoring and aroma additives may be added to the smoking tobaccomaterials of substitute therefor either separately or in admixture withone or more of the ether carboxaldehydes and/or ether carbinols of ourinvention as follows:

(i) Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

β-Damascenone;

β-Damascone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b)]furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

(ii) Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more of the ethercarboxaldehydes and/or ether carbinols prepared in accordance with theprocess of our invention, and, if desired, one or more of theabove-identified additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixture thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or spicy notes,we have found that satisfactory results are obtained if the proportionby weight of the sum total of one or more of the ether carboxaldehydesand/or ether carbinols is between 250 ppm and 1,500 ppm (0.025%-0.15%)of the active ingredients to the smoking tobacco material. We havefurther found that satisfactory results are obtained if the proportionby weight of the sum total of one or more of the ether carboxaldehydesand/or ether carbinols of our invention is between 2,500 and 15,000 ppm(0.25%-1.50%).

Any convenient method for incorporation of one or more of the eithercarboxaldehydes and/or ether carbinols prepared in accordance with theprocesses of our invention in the tobacco product may be employed. Thus,one or more of the ether carboxaldehydes and/or ether carbinols of ourinvention taken alone or along with other flavoring additives may bedissolved in a suitable solvent, such as ethanol, pentane, diethyl etherand/or other volatile organic solvents and the resulting solution mayeither be sprayed on the cured, cased and blended tobacco material orthe tobacco material may be dipped into such solution. Under certaincircumstances, a solution containing one or more of the ethercarboxaldehydes and/or ether carbinols of our invention taken alone ortaken further together with other flavoring additives as set forthabove, may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product, or itmay be applied to the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the smokingtobacco or substitute therefor need be treated and the thus treatedtobacco may be blended with other tobaccos before the ultimate tobaccoproduct is formed. In such cases, the tobacco treated may have one ormore of the ether carboxaldehydes and/or ether carbinols of ourinvention in excess of the amounts of concentrations above-indicated sothat when blended with other tobaccos, the final product will have thepercentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic Burley tobacco is sprayed with a 20% ethyl alcoholsolution of a 50:35:15 weight:weight:weight mixture of compoundscontaining materials having the following structures (in the orderstated): ##STR84## respectively in an amount to provide the tobaccocomposition containing 800 ppm by weight of the above-mentioned ethercarboxaldehydes and/or ether carbinols on a dry basis.

Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarettes,when treated as indicated, have a desired and pleasing aroma prior tosmoking which can be described as woody, incense-like, oriental, mintyand patchouli-like and, on smoking, in the main stream and in the sidestream as spicy, oriental-like, turkish tobacco-like, and woody with aslight mouth coating effect.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco, and pipe tobacco,other smoking tobacco products formed from sheeted tobacco dust or finesmay also be used. Likewise, one or more of the ether carboxaldehydesand/or ether carbinols of our invention can be incorporated withmaterials such as, filter tip materials, seam paste, packaging materialsand the like which are used along with tobacco to form a product adaptedfor smoking. Furthermore, one or more of the ether carboxaldehydesand/or ether carbinols of our invention can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and accordingly, by the term "tobacco" is used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise whether composed of tobacco plant parts orsubstituted materials or both.

The following Examples I-X serve to illustrate processes for preparingthe ether carboxaldehydes and/or ether carbinols of our invention. Theexamples following Example X are illustrative of the organolepticutilities of the ether carboxaldehydes and ether carbinols of ourinvention. All parts and percentages given herein are by weight unlessotherwise specified.

EXAMPLE I PREPARATION OF 4-(p-CUMENYLOXY)-3-METHYLBUTYRALDEHYDE

Reaction: ##STR85##

Into a 500 cc autoclave is placed

200 grams of the compound having the structure: ##STR86## and 0.1 gramof Rhodium acetoacetate dicarbonyl.

The autoclave is sealed and pressurized to 1,000 psig at 120° using a50:50 mole:mole mixture of carbon monoxide and hydrogen and maintainedat that pressure and temperature for a period for 14.5 hours. GLCanalysis indicates 83% product formed.

The reaction mass is cooled and the autoclave is opened. The contentsare filtered and the liquid material is distilled on a 2" splash columnyielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fractions                                 No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         97/103  133/140    3.5    18.3                                      2        104      140        3.0    27.8                                      3        134      158        2.4    47.1                                      4        140      180        4.0    39.5                                      ______________________________________                                    

Fractions 2, 3 and 4 are bulked and redistilled on a micro Vigreuxcolumn yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         65/      142/      3.4    2.9                                       2        75       145        3.4    3.2                                       3        73       148        3.4    3.0                                       4        70       150        3.4    2.3                                       5        98       155        3.4    7.6                                       6        95       157        3.4    7.6                                       7        80       164        3.6    11.5                                      8        94       172        3.6    1.5                                       9        104      193        3.6    3.1                                       10       100      200        3.6    5.7                                       11       80       220        3.6    3.2                                       ______________________________________                                    

FIG. 1 is the GLC profile for Fraction 4 of the foregoing distillation.

The peak indicated by reference numeral "10" is the peak for thecompound having the structure: ##STR87##

FIG. 2 is the NMR spectrum for the peak indicated by reference numeral"10" on FIG. 1 for the compound having the structure: ##STR88##(Conditions: CFCl₃ solvent; Field strength: 100 MHz).

EXAMPLE II PREPARATION OF 4(p-CUMENYLOXY)-3-METHYL-1-BUTANOL

Reaction: ##STR89##

Into a one liter reaction flask is placed 56.7 grams (1.5 moles) ofsodium borohydride and 200 ml of anhydrous isopropyl alcohol. Over aperiod of 45 minutes, 225 grams of the aldehyde having the structure:##STR90## is added to the reaction mass. The reaction mass is maintainedat 20° C. for a period of three hours with stirring. At the end of thethree hour period, the reaction mass is filtered and the filtrate iswashed with water until neutral. The crude reaction mass is thendistilled through a 2" splash column followed by a fractionaldistillation through a micro Vigreux column. The distillation throughthe micro Vigreux column yields the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         65      142        3.4    2.9                                       2        75       145        3.4    3.2                                       3        73       148        3.4    3.0                                       4        70       150        3.4    2.3                                       5        98       155        3.4    7.6                                       6        95       157        3.4    7.6                                       7        80       164        3.6    11.5                                      8        94       172        3.6    1.5                                       9        104      193        3.6    3.1                                       10       100      200        3.6    5.7                                       11       80       220        3.6    3.2                                       ______________________________________                                    

FIG. 3A is the GLC profile for the crude reaction product containing thecompound having the structure: ##STR91##

FIG. 3B is the GLC profile for fraction 5 of the foregoing distillationcontaining the compound having the structure: ##STR92##

FIG. 4 is the NMR spectrum for the peak indicated by reference "50" ofthe GLC profile of FIG. 3B for the compound having the structure:##STR93## (Conditions: Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE III PREPARATION OF 4-(2-BORNYLOXY)BUTYRALDEHYDE

Reaction: ##STR94##

Into a 500 ml autoclave are placed the following ingredients:

Isobornyl allyl ether having the structure:

    ______________________________________                                         ##STR95##            194 grams (1 mole)                                      Triphenylphosphine    2.0 grams                                               Rhodium Chloride-mono-carbonyl-                                                                     0.2 grams                                               triphenylphosphine                                                            Toluene               50.0 ml                                                 ______________________________________                                    

The autoclave is sealed and pressurized to 500 psig using a 50:50mole:mole mixture of carbon monoxide and hydrogen. The autoclave isheated to 200° and maintained at 500-700 psig for a period of 13 hours.At the end of the 13 hour period, the autoclave is cooled and openedyielding 462.9 grams of product (including toluene).

The reaction product is then distilled through a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         119/     165/      4.0    13.9                                      2        125      175        3.0    16.1                                      3        156      244        3.0    17.7                                      4        195      284        3.0    13.0                                      ______________________________________                                    

Fractions 2, 3 and 4 are bulked and redistilled through a spinning bandcolumn yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        /94      /134       2.8    9.7                                       2        95       140        2.6    8.7                                       3        62       147        2.6    3.5                                       4        102      163        2.4    2.8                                       5        114      178        2.4    3.3                                       6        70       194        2.8    5.9                                       7        64       240        2.9    4.4                                       ______________________________________                                    

The resulting product contains 70 percent by weight of the compoundhaving the structure: ##STR96## and 30 percent by weight of the compoundhaving the structure: ##STR97##

FIG. 5 is the GLC profile of bulked fractions 2-4 of the firstdistillation. This material contains a mixture of compounds having thestructures: ##STR98##

FIG. 6 is the GLC profile for fraction 5 of the spinning anddistillation and contains the compounds having the structures: ##STR99##

FIG. 7 is the NMR spectrum for the mixture of compounds containing 70percent by weight of the compound having the structure: ##STR100## and30 percent by weight of the compound having the structure: ##STR101##(Conditions: CFCl₃ solvent; 100 MHz field strength).

EXAMPLE IV PREPARATION OF 4-(2-BORNYLOXY)-1-BUTANOL)

Reaction: ##STR102##

Into an one liter reaction flask equipped with stirrer, thermometer,reflux condenser and heating mantel is placed 200 ml of anhydrousisoproply alcohol and 56.7 grams (1.5 moles) of sodium borohydride. Theresulting mixture is heated to reflux and during refluxing, over a 45minute period, the aldehyde having the structure: ##STR103## producedaccording to Example III is added to the reaction mass. The reactionmass is then continued to be stirred at reflux for a period of threehours. At the end of the three hour period, the reaction mass is cooledto room temperature and the undissolved sodium borohydride is filtered.The reaction mass is then washed with water until neutral. The crudereaction mass, weighing 309.3 grams, is then rushed over through a 2"splash column yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        95/       119/      1.3    2.2                                       2        100      120        1.4    9.4                                       3        104      130        1.4    30.8                                      4        105      135        1.5    34.4                                      5        107      145        1.6    37.0                                      6        106      173        1.7    16.3                                      7        106      179        1.7    1.0                                       ______________________________________                                    

FIG. 8 is GLC profile for the crude reaction product containing thecompounds having the structure: ##STR104##

FIG. 9 is the GLC profile for fraction 2 of the foregoing distillationproduct containing the compound having the structure: ##STR105##

FIG. 10 is the NMR spectrum for the compound having the structure:##STR106## produced according to this Example (Conditions: Fieldstrength: 100 MHz; solvent: CFCl₃).

FIG. 11 is the infrared spectrum for the compound having the structure:##STR107## produced according to this Example.

EXAMPLE V PRODUCTION OF 4-(2-BORNLOXY)-1-BUTANOL

Reaction: ##STR108##

Into an one liter reaction flask equipped with stirrer, thermometer andreflux condenser is placed 500 grams of 1,4-butanediol and 15 grams ofborn trifluoride. The reaction mass is heated to 80° C. Over a period ofone hour, a mixture of 500 grams of camphene and 500 grams of1,4-butanediol is added to the reaction mass. During the additionperiod, the reaction mass is maintained at 79°-80° C. with stirring. Thereaction mass is continued to be stired at 80° C. for a period of sevenhours. At the end of the seven hour period, the reaction mass is washedwith water and extracted with toluene. The organic phase is thenseparated and is washed with saturated sodium carbonate solution. Thethus washed material is then dried over anhydrous sodium sulfate anddistilled on a 12" Goodloe column yielding the following fractions.

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        118/127  157/143    1.2/3  39                                        2        128      143        2.7    38                                        3        128      143        2.8    42                                        4        128      143        2.7    46                                        5        128      143        2.8    35                                        6        128      145        2.8    55                                        7        129      150        2.8    39                                        8        133      207        3.0    27                                        ______________________________________                                    

FIG. 12 is the GLC profile for crude reaction product for this Examplecontaining the compound having the structure: ##STR109##

FIG. 13 is the NMR spectrum for fraction 4 of the foregoing distillationproduct containing the compound having the structure: ##STR110##

EXAMPLE VI PREPARATION OF 4-(2-BORNYLOXY)2-BUTANOL

Reaction: ##STR111## Into a one liter reaction vessel equipped with astirrer, thermometer, reflux condenser and heating mantel is placed 340grams of t,3-butanidiol and 10 grams of bron trifluoride. The reactionmass is heated to 80° C. and while maintaining the reaction mass at 80°C., 340 grams of camphene is added over a two hour period. At the end ofthe camphene feeding period, the reaction mass is stirred at atemperature of 80° C. for a period of 18 hours.

After the 18 hour period, the reaction mass is quenched with water andthe reaction mass is washed with saturated sodium carbonate solutionuntil neutral. The aqueous phase is separated from the organic phase.The aqueous phase is extracted with toluene and the toluene extracts areadded to the organic phase. The resulting organic material is thencharged to an evaporator and the toluene solvent is recovered.

The resulting product is distilled on a column packed with splashsaddles yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         93/      127/      5.0    7.0                                       2        115      127        5.0    15.0                                      3        123      136        4.8    211.0                                     4        175      220        3.8    190.0                                     ______________________________________                                    

FIG. 14 is the GLC profile for the crude reaction product containing thecompound having the structure: ##STR112##

FIG. 15 is the NMR spectrum for fraction 2 of the foregoing distillationproduct containing the compound having the structure: ##STR113##(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE VII PREPARATION OF 4-(2-BORNYLOXY)-2-BUTEN-1-OL

Reaction: ##STR114##

Into a two liter reaction vessel equipped with stirrer, thermometer,heating mantel and reflux condenser is placed 1000 grams (7.35 moles) of2-pentene-1,4-diol and 15 grams of boron trifluoride etherate. Thereaction mass is then heated to 80° C. Over a period of two hours whilemaintaining the reaction mass at 80° C., 500 grams (3.7 moles) ofcamphene is added. The reaction is continued to be stirred at 80° C. fora period of 12.5 hours after the feeding of the camphene.

At the end of the 12.5 hour period, the reaction mass is cooled to roomtemperature, quenc-ed with water and neutralized with saturated sodiumcarbonate. The organic phase is then distilled on a 2" splash columnpacked with saddles yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         80/102  118/124    1.2    14.0                                      2        110      126        1.2    19.0                                      3        120      131        1.2    64.0                                      4        130      143        1.2    205.0                                     5        155      180        1.2    142.0                                     6        170      220        1.2    60.0                                      ______________________________________                                    

Fractions 2-5 are bulked and redistilled on a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        128/130  153/151    2.6    16.0                                      2        130      146        2.6    18.0                                      3        131      147        2.6    20.0                                      4        131      147        2.6    19.0                                      5        131      147        2.6    27.0                                      6        131      147        2.6    22.0                                      7        131      147        2.6    18.0                                      8        131      147        2.6    25.0                                      9        131      147        2.6    26.0                                      10       131      148        2.6    23.0                                      11       131      149        2.6    27.0                                      12       132      150        2.6    20.0                                      13       131/132  150/152    2.5    21.0                                      14       132      155        2.5    26.0                                      15       132      162        2.5    25.0                                      16       132      187        2.5    20.0                                      17       139      207        2.5    13.0                                      18       155      210        2.5    8.0                                       ______________________________________                                    

FIG. 16 is the GLC profile for the crude reaction product containing thecompound having the structure: ##STR115## (Conditions: SE 30 columnprogrammed at 100°-200° C. at 8° C. per minute).

FIG. 17 is the NMR spectrum for fraction 4 of the foregoing distillationproduct containing the compound having the structure: ##STR116##

EXAMPLE VIII PREPARATION OF4-[1,3-DIMETHYL-2-BUTENYL)OXY]-3-METHYLBUTYRALDEHYDE

Reaction: ##STR117##

Into a high-pressure oxo-reactor is placed 98 grams of the methallylether having the structure: ##STR118## 0.3 grams ofrhodium-chlorocarbonyl (triphenyl phosphine), 3 grams of triphenylphosphine and 300 ml of anhydrous toluene. The oxo-reactor is sealed,heated to 130° C. and pressurized to 1000 psig with a 50:50 mole:molemixture of carbon monoxide and hydrogen. The oxo-reactor is stirred fora period of one hour at 1000 psig and 130° C. and then the temperatureis raised to 140° C. The oxo-reactor is then stirred for a period offour hours at 140° C. The reaction mass is then cooled to roomtemperature, and the reactor is opened. The reaction product is thenfiltered. The filtrate weighs 355.5 grams. The filtrate is thendistilled on a 2" splash column yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        /53      /63        10.4   58.2                                      2        52       67         10.0   67.5                                      3        50       127        9.5    70.1                                      4        61       97         7.0    8.9                                       5        89       95         7.0    12.2                                      6        82       98         7.9    10.4                                      7        85       97         4.9    17.6                                      8        80       105        3.7    12.5                                      9        78       123        3.6    10.9                                      10       80       137        3.6    7.5                                       11       86       210        3.8    6.9                                       ______________________________________                                    

FIG. 18 is the GLC profile for fraction 4 of the foregoing distillationproduct containing the compound having the structure: ##STR119##

FIG. 19 is the NMR spectrum for fraction 8 of the foregoing distillationcontaining the compound having the structure: ##STR120## (Conditions:Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE IX PREPARATION OF4-[(1,3-DIMETHYL-2-BUTENYL)OXY]-3-METHYL-1-BUTANOL

Reaction: ##STR121##

Into a 250 cc reaction vessel equipped with stirrer, thermometer, refluxcondenser and heating mantel is placed 10 grams of sodium borohydrideand 100 ml anhydrous isopropyl alcohol.

While maintaining the reaction mass at room temperature, 66.5 grams ofthe aldehyde produced according to Example VIII, supra, containing thecompound having the structure: ##STR122## is added to the reaction massover a period of two hours. During the addition of this material, thereaction mass temperature rises to 40° C. as a result of the exothermicreaction. The reaction mass is cooled and maintained at 40° C. withstirring for a period of four hours. At the end of the four hour period,the reaction mass is cooled to room temperature. A 5% aqueous solutionof hydrochloric acid is added to the reaction mass. The reaction mass isthen washed with water followed by a saturated sodium carbonate solutionuntil neutral. The resulting reaction mass is then distilled on a 2"splash column yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         83/      94/       1.6    3.0                                       2        81       86         1.3    4.0                                       3        81       86         1.3    5.1                                       4        90       96         2.2    2.5                                       5        90       110        2.0    10.0                                      6        94       210        2.0    5.9                                       ______________________________________                                    

FIG. 20 is the GLC profile for the crude reaction product containing thecompound having the structure: ##STR123##

FIG. 21 is the NMR spectrum for fraction 4 of the foregoing distillationproduct containing the compound having the structure: ##STR124##(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE X PREPARATION OF 3-METHYL-4-PHENOXY-BUTANAL

Reaction: ##STR125##

Into a high-pressure oxo-reactor are placed the following materials:

Allyl ether having the structure:

    ______________________________________                                         ##STR126##         148    grams (1 mole)                                     Triphenyl phosphine 6      grams                                              Rhodium cholorol carbonyl                                                                         0.6    grams                                              (triphenyl phosphine)                                                         ______________________________________                                    

The oxo-reactor is sealed, heated to 140° C. and pressurized with a50:50 mole:mole mixture of hydrogen and carbon monoxide. The reactionmass is stirred while maintaining the temperature of 140° C. andmaintaining the pressure at 1000 psig for a period of ten hours.

At the end of the ten hour period, the oxo-reactor is cooled, opened andthe contents removed and filtered.

The resulting filtrate is then distilled on a 2" splash column yieldingthe following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         35/      45/       1.6    21.3                                      2        72       100        1.6    9.2                                       3        100      108        1.6    35.1                                      4        99       108        1.5    51.8                                      5        97       108        1.3    50.1                                      6        95       135        1.3    32.2                                      ______________________________________                                    

Fractions 2-6 are bulked and redistilled on a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         50/58   112/117    2.8/3.0                                                                              6.6                                       2        62       112        1.6    10.0                                      3        94       127        1.6    12.7                                      4        94       128        1.5    14.2                                      5        88       128        1.2    12.1                                      6        88       128        1.2    13.0                                      7        100      128        1.2    8.4                                       8        104      127        2.3    10.4                                      9        100      128        2.0    17.9                                      10       104      131        2.3    18.0                                      11       102      147        2.3    14.8                                      12       80       100        2.3    8.9                                       ______________________________________                                    

FIG. 22A is the GLC profile for the crude reaction product containingthe compound having the structure: ##STR127##

FIG. 22B is the NMR spectrum for the compound having the structure:##STR128## (Conditions: Solvent: CFCl₃ ; Field strength: 100 MHz).

EXAMPLE XI PINE FRAGRANCE

The following pine fragrance formulations are prepared:

    ______________________________________                                                        Parts By Weight                                               Ingredients       IX-A     IX-B     IX-C                                      ______________________________________                                        Isobornyl acetate 100      100      100                                       Camphor           10       10       10                                        Terpineol         25       25       25                                        Fir balsam absolute                                                                             20       20       20                                        (50% in diethyl phthalate)                                                    Coumarin          4        4        4                                         Linalool          30       30       30                                        Frenchyl alcohol  10       10       10                                        Anethol           12       12       12                                        Lemon terpenes washed                                                                           50       50       50                                        Borneol           5        5        5                                         Galbanum oil      5        5        5                                         Turpentine Russian                                                                              150      150      150                                       Eucalyptol        50       50       50                                        2,2,6-trimethyl-1-cyclohexene-1-                                                                12       12       12                                        carboxaldehyde                                                                Maltol (1% in diethyl phthalate)                                                                5        5        5                                         Compound having the structure:                                                                  28       0        0                                          ##STR129##                                                                   prepared according to                                                         Examples IV or V                                                              Compound having the structure:                                                                  0        28       0                                          ##STR130##                                                                   prepared according to                                                         Example VI                                                                    Compound having the structure:                                                                  0        0        28                                         ##STR131##                                                                   prepared according to                                                         Example IX                                                                    ______________________________________                                    

The compound having the structure: ##STR132## imparts to the pineformulation an intense minty patchouli aroma and causes it to haveintense patchouli topnotes. Accordingly, the pine formulation can bedescribed as "piney with an intense patchouli and minty aroma havingpatchouli topnotes".

The compound having the structure: ##STR133## imparts to this pineyformulation a very natural-like incense and cedarwood aroma.Accordingly, the formulation thus prepared can be described as "naturalpiney with cedarwood-like and incense topnotes".

The compound having the structure: ##STR134## imparts to this pineyformulation a camphoraceous, woody, lavender, spicy and floral aromawith patchouli and rosey undertones. Accordingly, the formulation can bedescribed from a perfumery standpoint as "piney with camphoraceouswoody, lavender, spicy, floral, patchouli and rosey undertones."

EXAMPLE XII FLORAL PERFUME COMPOSITIONS

The compound having the structure: ##STR135## produced according toExample II has an ozoney fresh air dried cloth-like, green, orange,nutty and woody aroma. This material has great warmth and richness andblends well with many floral concepts. It is a rather unique floral noteof great value to perfumery. Its use may be demonstrated by thefollowing floral fragrance whereby the compound having the structure:##STR136## is used to the extent of 5% by weight.

The compound having the structure: ##STR137## produced according toExample VIII imparts to this floral fragrance a herbaceous, stronggreen, leafy, peppery and spicy aroma with herbaceous, peppery, olibanumand diffusive amber-like undertones. The addition of 5% by weight of thecompound having the structure: ##STR138## imparts a very desirable spicyand green character.

The compound having the structure: ##STR139## imparts to the floralformulation a camphoraceous, woody, lavender and spicy aroma.

The compound having the structure: ##STR140## imparts to the floralformulation a herbaceous, sweet fruity, chamomile-like undertone.

All four of these products perform quite well in fragrances and arejudged to be very valuable fragrance materials:

    ______________________________________                                        FLORAL FRAGRANCE                                                                              "A"  "B"      "C"    "D"                                      ______________________________________                                        Citronellol       12.3   12.3     12.3 5.0                                    Geraniol          2.5    2.5      2.5  5.0                                    Amyl Cinnamic Aldehyde                                                                          24.6   24.6     24.6 5.0                                    Galaxolide ® 50 (Trademark                                                                  9.8    9.8      9.8  5.0                                    Tricyclic Isochroman of                                                       International Flavors &                                                       Fragrances Inc.)                                                              Vertenex High Cis (Cis-t                                                                        7.4    7.4      7.4  5.0                                    Butylcyclohexenyl Acetate;                                                    Para Isomer)                                                                  Rose Oxide        0.7    0.7      0.7  5.0                                    Cinnamic Alcohol  19.6   19.6     19.6 5.0                                    Aldehyde C-11 (n-Undecylenic                                                                    0.5    0.5      0.5  5.0                                    Aldehyde)                                                                     Aldehyde C-12 (n-Dodecyl                                                                        0.5    0.5      0.5  5.0                                    Aldehyde in 10% solution                                                      in diethyl phthalate)                                                         Citronellal (10% solution                                                                       0.5    0.5      0.5  5.0                                    in diethyl phthalate)                                                         Phenyl Ethyl Acetate                                                                            2.5    2.5      2.5  5.0                                    Ylang Oil         1.2    1.2      1.2  5.0                                    Indisan (Hydrogenated                                                                           3.7    3.7      3.7  5.0                                    derivative of reaction                                                        product of Camphene and                                                       Resorcinol)                                                                   Musk Ketone       5.0    5.0      5.0  5.0                                    Oakmoss Resin     0.5    0.5      0.5  5.0                                    Liatrix Absolute (10% in                                                                        2.5    2.5      2.5  5.0                                    diethyl phthalate)                                                            Vetiver Acetate   1.2    1.2      1.2  5.0                                    Diethyl Phthalate 5.0    5.0      5.0  5.0                                    Compound having the structure:                                                                  5.0    0        0    0                                       ##STR141##                                                                   produced according to                                                         Example II.                                                                   Compound having the structure:                                                                  0      5.0      0    0                                       ##STR142##                                                                   Compound having the structure:                                                                  0      0        5.0  0                                       ##STR143##                                                                   Compound having the structure:                                                                  0      0        0    5.0                                     ##STR144##                                                                   ______________________________________                                    

Thus, as a result of adding the compound having the structure:##STR145## the fragrance can be described as "floral with ozoney, freshair dried cloth-like, green and fresh orange undertones".

The fragrance produced by having the compound having the structure:##STR146## added thereto, can be described as "floral with herbaceousstrong green, leafy, pepper, spicy, olibanum and diffusive amberundertones".

The fragrance produced by having added thereto the compound having thestructure: ##STR147## can be described as "floral with camphoraceous,woody, lavender, spicy, patchouli and rosey undertones".

The fragrance having added thereto the compound having the structure:##STR148## can be described as "floral with herbaceous, sweet fruity,chamomile-like and caramellic undertones".

EXAMPLE XIII PREPARATION OF LILAC FRAGRANCE

The following mixture is prepared:

    ______________________________________                                        Hydroxcitronellal      22%                                                    Phenyl Ethyl Alcohol   12%                                                    Heliotropine           12%                                                    Linalool               8%                                                     Cinnamic Alcohol       4%                                                     Indole - 10% in Diethyl Phthalate                                                                    2%                                                     Benzyl Acetate         8%                                                     Anisic Alcohol         8%                                                     Coumarin - 10% in Diethyl Phthalate                                                                  4%                                                     Compound having the structure:                                                                       4%                                                      ##STR149##                                                                   prepared according to                                                         Example VII.                                                                  ______________________________________                                    

The compound having the structure: ##STR150## imparts to this lilacfragrance an interesting animalic sweaty lavender-like undertone.Accordingly, the fragrance can be described as "lilac with an animalicsweaty lavender-like undertone".

EXAMPLE XIV PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table III below. Each of the cosmetic powder compositions hasan excellent aroma as described in Table III below:

                  TABLE III                                                       ______________________________________                                        SUBSTANCE         AROMA DESCRIPTION                                           ______________________________________                                         ##STR151##       A nutty, woody, ozoney, fresh air dried cloth, green,                         orange aroma profile.                                        ##STR152##       A minty patchouli aroma with patchouli undertones.           ##STR153##       An incense aroma with cedarwood undertones.                  ##STR154##       An onion, garlic and laven- der aroma profile with                            oniony, animalic sweaty  undertones.                         ##STR155##       A herbaceous, strong green leafy, pepper and spicy                            aroma with herbaceous pep- pery olibanum and diffusive                        amber undertones.                                            ##STR156##       A camphoraceous, woody, lavender, spicy and floral                            aroma with patchouli and rosey undertones.                   ##STR157##       A herbaceous, sweet fruity, and chamomile-like aroma                          with caramellic undertones.                                 Fragrance of Example                                                                            A piney aroma with an intense                               XI(A).            patchouli and minty aroma                                                     having patchouli topnotes.                                  Fragrance of Example                                                                            A natural piney aroma with                                  XI(B).            cedarwood-like and incense                                                    topnotes.                                                   Fragrance of Example                                                                            A piney aroma with camphora-                                XI(C).            ceous, woody, lavender, spicy,                                                floral patchouli and rosey                                                    undertones.                                                 Perfume composition of                                                                          Floral with ozoney, fresh air                               Example XII(A).   dried cloth-like, green and                                                   orange undertones.                                          Perfume composition of                                                                          Floral with herbaceous,                                     Example XII(B)    strong green, leafy,                                                          peppery, spicy, olibanum                                                      and diffusive amber                                                           undertones.                                                 Perfume composition of                                                                          Floral with camphoraceous,                                  Example XII(C)    woody, lavender, spicy,                                                       patchouli and rosey                                                           undertones.                                                 Perfume composition of                                                                          Floral with herbaceous,                                     Example XII(D)    sweety fruity, chamomile-                                                     like and caramellic                                                           undertones.                                                 Perfume composition of                                                                          Lilac with an animalic,                                     Example XIII      sweaty, lavender-like                                                         undertones.                                                 ______________________________________                                    

EXAMPLE XV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with aromas as set forth in Table III ofExample XIV (which detergents are prepared from Lysine salt of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Pat. No.3,948,818 issued on Apr. 6, 1976 the specification for which isincorporated by reference herein) are prepared containing each of thesubstances set forth in Table III of Example XIV, supra. They areprepared by adding and homogeneously mixing the appropriate quantity ofperfumery substance as set forth in Table III of Example XIV in theliquid detergent. The detergents all possess aromas as set forth inTable III of Example XIV, the intensity increasing with greaterconcentrations of perfumery substance of Table III of Example XIV,supra.

EXAMPLE XVI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The perfume substances of Table III of Example XIV, supra, areincorporated into colognes at concentrations of 1.5%, 2.0%, 2.5%, 3.0%and 4.0% in 80%, 85% and 90% aqueous ethanols; and into a handkerchiefperfume composition at concentrations of 10%, 15%, 20%, 25% and 30% (in85%, 90% and 95% aqueous ethanols). Distinct and definitive aromas asset forth in Table III of Example XIV are imparted to the cologne and tothe handkerchief perfume compositions.

EXAMPLE XVII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a non-ionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Letters Patent No. 985,190 issued on Mar. 9, 1976 thedisclosure of which is incorporated by reference herein) is mixed with0.15 grams of each of the substances set forth in Table III of ExampleXIV, supra, until substantially homogeneous compositions are obtained.These compositions have excellent aromas as set forth in Table III ofExample XIV.

EXAMPLE XVIII PREPARATION OF SOAP

Each of the perfumery substances of Table III of Example XIV areincorporated into soap (LVU-1) at 0.1% by weight of each substance.After two weeks in the oven at 90° F. each of the soaps showed no visualeffect from the heat. Each of the soaps manifested an excellent aroma asset forth in Table III of Example XIV, supra.

EXAMPLE XIX PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips (IVORY®, registered trademark of theProcter & Gamble Co. of Cincinnati, Ohio) are mixed individually withone gram each of the perfumery substances of Table III of Example XIV,supra, until a homogeneous composition is obtained. The homogeneouscomposition is then treated under three atmospheres pressure at 180° C.for a period of three hours and the resulting liquid is placed into asoap mold. The resulting soap cakes, on cooling, manifest excellentaromas as set forth in Table III of Example XIV, supra.

EXAMPLE XX PREPARATION OF A SOLID DETERGENT COMPOSITION

A detergent is prepared from the following ingredients according toExample I of Canadian Letters Patent No. 1,007,948 the specification forwhich is incorporated by reference herein):

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        "Neodol 45-II " (a C.sub.14 -C.sub.15                                                           12                                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate  55                                                          Sodium citrate    20                                                          Sodium sulfate, water                                                                           q.s.                                                        brighteners                                                                   ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed separately with 0.15 grams of each of theperfume substances of Table III of Example XIV, supra. The detergentsamples each have excellent aromas as set forth in Table III of ExampleXIV, supra.

EXAMPLE XXI

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the specification for which is incorporated by referenceherein), a non-woven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared, wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper"),

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.);

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of one of the perfume substances of of Table III of ExampleXIV, supra.

A fabric softening composition prepared as set forth above having theabove aroma characteristics as set forth in Table III of Example XIV,supra, essentially consists of a substrate having a weight of about 3grams per 100 square inches, a substrate coating of about 1.85 grams per100 square inches of substrate and an outer coating of about 1.4 gramsper 100 square inches of substrate, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight ofsubstrate. The aroma set forth in Table III of Example XIV is impartedin a pleasant manner to the headspace in the dryer on operation thereof,using said dryer-added fabric softening non-woven fabric.

EXAMPLE XXII FLAVOR COMPOSITION

The following basic walnut flavor formulation is prepared:

    ______________________________________                                        INGREDIENTS          PARTS BY WEIGHT                                          ______________________________________                                        Ethyl-2-Methyl Butyrate                                                                            10                                                       Vanillin             40                                                       Butyl Valerate       40                                                       2,3-Diethyl Pyrazine 5                                                        Methyl Cyclopentenolone                                                                            80                                                       Benzaldehyde         60                                                       Valerian Oil Indian  0.5                                                      (1% in 95% aqueous ethanol alcohol)                                           Propylene Glycol     764.5                                                    ______________________________________                                    

The compound having the structure: ##STR158## prepared according to theprocess of Example VI is added to the above formulation at the rate of1.5%. The formulation is compared to a formulation which does not havethe compound having the structure: ##STR159## The formulation containingthe compound having the structure: ##STR160## has a woody-balsamic,fresh walnut kernel and walnut skin-like taste and, in addition, has afuller mouth-feel and longer lasting taste. The flavor that has added toit, the compound having the structure: ##STR161## is preferred by agroup of flavor panelists not associated with the assignee of theinstant application or the inventorship entity and they consider it tobe a substantially improved walnut flavor.

EXAMPLE XXIII ORANGE FLAVOR FORMULATION

An orange flavor formulation is prepared by admixing:

    ______________________________________                                        INGREDIENTS    PARTS BY WEIGHT                                                ______________________________________                                        Natural orange oil                                                                           13.00                                                          Acetaldehyde   1.50                                                           Ethyl acetate  0.10                                                           Ethyl butyrate 0.50                                                           Propanol       0.10                                                           trans-2-Hexenal                                                                              0.10                                                           Ethyl alcohol (95%)                                                                          60.00                                                          Fusel oil      0.05                                                           Propylene glycol                                                                             24.65                                                          ______________________________________                                    

This is denominated Flavor A. A second formulation, Flavor B is preparedby adding the compound having the structure: ##STR162## preparedaccording to Example II to a portion of Flavor A and the ration of twoparts to 100 parts of Flavor A.

Each of Flavors A and B is added in the amount of 2 ounces per gallon of32° Baume sugar syrup to produce a syrup for combination with water toform a drink. The beverage prepared using Flavor A is a passable orangebeverage of good character, flavor and intensity.

The beverage prepared using Flavor B has a much improved flavor. Theimprovement contributed by the compound having the structure: ##STR163##is due to: i. a greater degree of natural character of freshly squeezedorange juice

ii. an increase in the pulplike notes and

iii. greater orange juice flavor depth.

EXAMPLE XXIV

0.5 Grams of the mixture:

    ______________________________________                                        INGREDIENTS          PARTS BY WEIGHT                                          ______________________________________                                        Dimethyl sulfide     4                                                        Methyl propyl disulfide                                                                            25                                                       Methyl propenyl disulfide                                                                          2                                                        Dipropyl disulfide   12                                                       Propyl propenyl disulfide                                                                          8                                                        Diallyl disulfide    1                                                        Compound having the structure                                                                      12                                                        ##STR164##                                                                   prepared according to Example VII                                             ______________________________________                                    

is imulsified in a solution containing the following materials:

100 grams gum arabic

300 grams water

0.5 grams 20 percent solution in ethanol of butylated hydroxy anisole.

The resultant emulsion is spray-dried in a Bowen Lab. Model spray-drier,inlet temperature 500° F., outlet temperature 200° F. 12 Grams of thisspray-dried material is mixed with 29.2 grams of the following soupbase:

    ______________________________________                                        INGREDIENTS       PARTS BY WEIGHT                                             ______________________________________                                        Fine ground sodium chloride                                                                     35.62                                                       Hydrolized vegetable protein                                                                    27.40                                                       [4 BE:Nestle's]                                                               Mono sodium glutamate                                                                           17.81                                                       Mono calcium glutamate                                                                          17.81                                                       Sucrose           10.96                                                       Beef Fat          5.48                                                        Sethness caramel color                                                                          2.73                                                        [powder B & C]                                                                ______________________________________                                    

The resultant mixture is then added to 12 ounces of boiling water and anexcellent onion-flavored soup is obtained which is comparative to thatcreated using natural onions or natural onion oil.

EXAMPLE XXV TOOTHPASTE

The compound having the structure: ##STR165## prepared according toExample IV or V is incorporated at the rate of 0.1% in toothpaste(Colgate MFP Fluoride Gel "Winterfresh" manufactured by the ColgatePalmolive Corporation of New York, N.Y.) and evaluated by a panel ofnine people for its aroma characteristics against a control without theaddition of the compound having the structure: ##STR166## The entirepanel unanimously preferred the toothpaste with the compound having thestructure: ##STR167## as having a fresher, more cooling aroma withpatchouli overtones and oriental, incense, musky and sandalwood nuancesthan the control.

A small group of panelists (3 in number) brushed their teeth with thesame toothpaste using 0.1%, 0.2% and 0.5% of the compound having thestructure: ##STR168## produced according to Example III or IV brushingtheir teeth at three hour intervals. All members of the panel are of theopinion that the clean, fresh sensation lasted longer with thetoothpaste containing the compound having the structure: ##STR169## thanwithout it. In addition, all members of the panel state that the bitterafter-taste related to the saccharin in the toothpaste is depressed anda more pleasant after-taste is created. No off-note is created by thecompound having the structure: ##STR170## In addition, when the compoundhaving the structure: ##STR171## is used at a level 0.5% the sameresults are obtained with no off-note created by the compound having thestructure: ##STR172##

Therefore, it is concluded that the compound having the structure:##STR173## is effective in improving oral hygiene products includingtoothpaste, mouthwash, mouth sprays and sugar-based tablets and inaddition, chewing gum.

The compound having the structure: ##STR174## improves the organolepticproperties of toothpaste, chewing gum, mouthwash, mouth sprays andsugar-based mouth freshener tablets:

(i) by adding fresher topnotes

(ii) by enhancing the menthol-like cooling notes (without using menthol)

(iii) by extending the fresh after-taste without having an effectsimilar to that of chloroform (without the use of chloroform), and

(iv) by imparting oriental incense, musky and sandalwood and patchoulinuances to the toothpaste.

The foregoing effects are unexpected, unobvious and advantageous.

EXAMPLE XXVI(A) FLAVOR PREPARATION

The following flavor formulation is prepared by admixing the ingredientsin the proportion set forth below:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Clove oil            1.0                                                      Cardamon oil         0.1                                                      Spearmint oil        5.0                                                      Anethol              2.0                                                      Compound having the structure:                                                                     4.0                                                       ##STR175##                                                                   produced according to                                                         Examples IV or V.                                                             Peppermint oil, redistilled                                                                        83.9                                                     Prenyl methyl carbonate                                                                            2.0                                                      ______________________________________                                    

EXAMPLE XXVI(B)

Ten parts by weight of 50 Bloom pigskin gelatin is added to ninety partsby weight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin completely dissolves and the solution is cooled to120° F. Twenty parts by weight of the flavor of Part (A) supra is addedto the solution which is then homogenized to form an emulsion, having aparticle size typically in the range of 2-5 microns. The material iskept at 120° F. under which conditions the gelatin will not gel.

Coacervation is induced by adding, slowly and uniformly 40 parts byweight of a 20% aqueous solution of sodium sulfate. During coacervation,the gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of a 7% aqueous solution of sodium sulfate at 65° F. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXVI(C)

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                            Liquid flavor composition of                                                                         48.4                                                   Part (A) supra                                                                Cab-O-Sil M-5 (brand of silica                                                                       3.2                                                    produced by the Cabot Corporation                                             of 125 High Street, Boston, Mass. 02110                                       Physical properties:                                                      Surface Area:   200 m.sup.2 /gm.                                              Nominal particle size:                                                                        0.012 microns                                                 Density:        2.3 lbs/cu. ft.                                               ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid flavor composition of Part (A)with vigorous stirring thereby resulting in a viscous liquid. 48.4 partsby weight of the powder flavor composition produced according to Part(B) supra, is then blended into said viscous liquid with stirring at 25°C. for a period of 30 minutes resulting in a thixotropic sustainedrelease patchouli-like and incense/ethereal/"cooling effect" flavoredcomposition.

EXAMPLE XXVII CHEWING GUM

One hundred parts by weight of chicle are mixed with four parts byweight of the flavor prepared in accordance with Example XXVI. Threehundred parts of sucrose and one hundred parts of corn syrup are added.Mixing is effected in a ribbon blender with jacketed side walls of thetype manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long-lasting,patchouli-like and incense/cooling/freshening flavor.

EXAMPLE XXVIII TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Group "A"                                                                     Glycerine            30.200                                                   Distilled water      15.325                                                   Sodium benzoate      0.100                                                    Saccharin sodium     0.125                                                    Stannous fluoride    0.400                                                    Group "B"                                                                     Calcium carbonate    12.500                                                   Dicalcium phosphate (dihydrate)                                                                    37.200                                                   Group "C"                                                                     Sodium N--lauroyl sarcosinate                                                                      2.000                                                    (foaming agent)                                                               Group "D"                                                                     Flavor materials of Example XXVI                                                                   1.200                                                    ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogenous gel.

3. The powders of Group "B" are added to the gel while mixing until ahomogenous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenizedand finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant patchouli-like and incense/cooling/freshening flavorof constant strong intensity throughout said procedure (1-1.5 minutes).

EXAMPLE XXIX TOBACCO FLAVOR FORMULATION

Cigarettes are produced using the following tabacco formulation:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           H.sub.2 O       5.3                                                           ______________________________________                                    

At the rate of 0.2% , the following tobacco flavor formulation isapplied to all of the cigarettes produced with the above tobaccoformulation.

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Ethyl Butyrate   .05                                                          Ethyl Valerate   .05                                                          Maltol           2.00                                                         Cocoa Extract    26.00                                                        Coffee Extract   10.00                                                        Ethyl Alcohol (95%)                                                                            20.00                                                        H.sub.2 O        41.90                                                        ______________________________________                                    

To 50% of the cigarettes, 10 and 20 ppm of the compound having thestructure: ##STR176## are added. These cigarettes are hereinafter called"experimental" cigarettes and the cigarettes without the compound havingthe structure: produced according to Example VI are hereinafter called"control" cigarettes. The control and experimental cigarettes are thenevaluated by paired comparison and the results are as follows:

a. In aroma, the experimental cigarettes are found to be more aromaticwith a woody, incense, oriental and patchouli aroma and taste.

b. In smoke flavor, the experimental cigarettes are found aromatic, moresweet, more bitter, richer and slightly less harsh in the mouth and morecigarettes tobacco-like than the control cigarettes with woody, incense,oriental and patchouli-like aroma and taste nuances.

In summary, the experimental cigarettes containing 20 ppm is thecompound having the structure: ##STR177## produced according to ExampleVI are found to be woody, incense, oriental and patchouli-like andturkish tobacco-like in the main stream and in the side stream.

All cigarettes both control and experimental are evaluated for smokeflavor with 20 mm cellulose acetate filters.

A similar effect occurs when using the compound having the structure:##STR178## produced according to Examples IV or V.

What is claimed is:
 1. An ether carbinol composition comprising thecompound having the structure: ##STR179## produced according to theprocess of reacting camphene having the structure: ##STR180## and1,3-butane diol having the structure: ##STR181## in the presence of aLewis acid catalyst at a temperature in the range of from about 60° C.up to about 100° C.; at a pressure in the range of from about oneatmosphere up to about ten atmospheres; the time of reaction being fromabout two hours up to about twenty hours; the mole ratio of1,3-dihydroxybutane having the structure: ##STR182## to camphene varyingfrom about 1:2 up to about 3:1 and then recovering the resulting productby means of fractional distillation.
 2. The product of claim 1 whereinin the process for preparing said product, the Lewis acid catalyst isborontrifluoride etherate.